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Method for synthesizing aromatic nitrile with arylboronic acid

An arylboronic acid and aromatic nitrile technology, which is applied in the field of aromatic nitrile compound synthesis, can solve the problems of high cost and high toxicity of cyanating reagents, and achieve the effects of improving greenness, low toxicity and reducing production cost.

Inactive Publication Date: 2012-02-22
HENAN UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] The purpose of the present invention is to provide a method for synthesizing aromatic nitriles from arylboronic acids, which solves the problems of high cost and high toxicity of cyanide reagents in the current method

Method used

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  • Method for synthesizing aromatic nitrile with arylboronic acid
  • Method for synthesizing aromatic nitrile with arylboronic acid
  • Method for synthesizing aromatic nitrile with arylboronic acid

Examples

Experimental program
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Effect test

Embodiment 1

[0029] Under nitrogen protection, add catalyst (0.3mmol Cu(OAc) 2 ·H 2 O, 0.01 mmol Pd(OAc) 2 ), 1mmol K 2 CO 3 , 1mmol phenylboronic acid, 0.5 mmol K 4 [Fe(CN) 6 ], 1 mmol I 2 and 1.5 mL dimethyl sulfoxide, sealed the reaction vessel and placed it in an oil bath preheated to 160°C, and reacted for 6 hours under magnetic stirring. After the reaction, cool the reaction system to room temperature, add 1 mL of dichloromethane solution of phenylacetonitrile (concentration: 0.7 mmol / mL) as an internal standard, stir until mixed evenly, and let stand. The clear solution in the upper layer was absorbed, and the product was quantified by gas chromatography, and the yield of benzonitrile was 89%. The product was purified by column chromatography, using mass spectrometry, 1 H-NMR and 13 C-NMR confirmed the structure of the product. Benzonitrile (C 7 h 5 N) mass spectrometry (see figure 1 ): The theoretical value of the molecular ion peak (M+) is 103.04, and the measured va...

Embodiment 2

[0031] Under the protection of nitrogen, add 0.3mmol Cu(OAc) to the reaction vessel successively 2 ·H 2 O, 0.01 mmol Pd(OAc) 2 , 1 mmol K 2 CO 3 , 1mmol p-tolueneboronic acid, 0.5 mmol K 4 [Fe(CN) 6 ], 1 mmol I 2and 1.5 mL dimethyl sulfoxide, sealed the reaction vessel and placed it in an oil bath preheated to 160°C, and reacted for 6 hours under magnetic stirring. After the reaction, cool the reaction system to room temperature, add 1 mL of dichloromethane solution of phenylacetonitrile (concentration: 0.7 mmol / mL) as an internal standard, stir until mixed evenly, and let stand. The clear solution in the upper layer was sucked, and the product was quantified by gas chromatography, and the yield of p-methylbenzonitrile was 74%. The product was purified by column chromatography, using mass spectrometry, 1 H-NMR and 13 C-NMR confirmed the structure of the product. p-Toluonitrile (C 8 h 7 N) mass spectrometry (see Figure 4 ): The theoretical value of the molecular i...

Embodiment 3

[0033] Under the protection of nitrogen, add 0.3mmol Cu(OAc) to the reaction vessel successively 2 ·H 2 O, 0.01 mmol Pd(OAc) 2 , 1 mmol K 2 CO 3 , 1mmol m-methylphenylboronic acid, 0.5 mmol K 4 [Fe(CN) 6 ], 1 mmol I 2 and 1.5 mL dimethyl sulfoxide, sealed the reaction vessel and placed it in an oil bath preheated to 160°C, and reacted for 6 hours under magnetic stirring. After the reaction, cool the reaction system to room temperature, add 1 mL of dichloromethane solution of phenylacetonitrile (concentration: 0.7 mmol / mL) as an internal standard, stir until mixed evenly, and let stand. The clear solution in the upper layer was absorbed, and the product was quantified by gas chromatography, and the yield of m-methylbenzonitrile was 76%. The product was purified by column chromatography and its structure was confirmed by mass spectrometry. m-methylbenzonitrile (C 8 h 7 N) mass spectrometry (see Figure 5 ): The theoretical value of the molecular ion peak (M+) is 117.0...

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Abstract

The invention belongs to the technical field of synthesis of an aromatic nitrile compound, in particular relates to a method for synthesizing aromatic nitrile with arylboronic acid. In the presence of catalysts, alkali and iodine, the aromatic nitrile is obtained through a reaction of the arylboronic acid and a cyanide reagent in organic solvent. The cyanide reagent is K4 [Fe (CN) 6] or K4 [Fe (CN) 6]*3H2O which is small in toxicity and cheaper. The method for synthesizing the aromatic nitrile compound is low in production cost and free of highly toxic materials.

Description

technical field [0001] The invention belongs to the technical field of synthesis of aromatic nitrile compounds, in particular to a method for synthesizing aromatic nitriles from arylboronic acid. Background technique [0002] Aromatic nitrile compounds have a wide range of uses, not only important chemical intermediates, but also key components of some dyes, pesticides, and medicines. Taking arylboronic acid as the method for the one-step synthesis of aromatic nitrile of raw material at present has: (1) be the method for cyanide reagent with benzyl thiocyanate (see Org. Lett. 2006, 8 , 4331-4333); (2) The method using zinc cyanide as the cyanide reagent (see J. Am. Chem. Soc. 2010, 132 , 11389-11391); (3) The method using p-toluenesulfonyl nitrile as cyanide reagent (see Angew. Chem. Int. Ed. 2011, 50 , 519-522), (4) the method using cuprous cyanide as the cyanide reagent (see Adv. Synth. Catal. 2011, 353 , 291-294). Cyanide reagent is one of the main raw material...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B43/08C07C253/00C07C255/50C07C255/54C07C255/52C07D213/84C07D307/68C07D333/38
Inventor 任运来孙艳培田欣哲姚怀王键吉侯超东
Owner HENAN UNIV OF SCI & TECH
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